Olefin polymerization processes and products thereof

ABSTRACT

A novel loop/slurry olefin polymerization process is provided which produces ultra high molecular weight ethylene homopolymer.

BACKGROUND

This invention relates to olefin polymerization processes and theresultant polymer products.

Ultra high molecular weight olefin polymers such as polyethylene areuseful in many demanding and extremely critical applications, such ashuman joint replacements, gears, bullet proof vests, skis, and otherapplications. Since ultra high molecular weight the polymer cannot bepelletized after leaving the reactor, the polymer must be sold as afluff or a powder. Therefore, particle size and toughness of theresultant polymer is critical.

Many commercial methods are available to produce olefin polymers, suchas polyethylene. One of the most economical routes to most commercialgrades of olefin polymers is a loop/slurry process with a paraffindiluent wherein the polymerization process carried out at a temperaturelow enough that the resulting polymer is largely insoluble in thediluent. It is believed that commercially acceptable ultra highmolecular weight polyethylenes traditionally are made using a stirredtank process, in a heavy hydrocarbon diluent.

SUMMARY OF THE INVENTION

It is an object of this invention to provide a very tough ultra highmolecular weight polyethylene.

It is a further object of this invention to provide an improved olefinpolymerization process.

It is yet another object of this invention to provide an improvedpolymerization process for preparing ultra high molecular weightpolyethylene.

In accordance with this invention, a process is provided to polymerizeethylene in a loop/slurry process using a Ziegler/Natta-type catalystsystem to produce a very tough ultra high molecular weight polyethylene.

In accordance with another embodiment of this invention, a very tough,ultra high molecular weight polyethylene is provided.

DESCRIPTION OF THE DRAWINGS

FIG. 1 shows three (3) molecular weight distributions obtained from sizeexclusion chromatography (SEC) of three different polyethylene samples."UHMWPE" designates ultra high molecular weight polyethylene.

The x-axis, labeled "LOG M", is the log of the polyethylene molecularweight. The y-axis, labeled "DW/D(LOG M)", is the differential massfraction. Two curves, designated as "600 Gallon Reactor" and "23 GallonReactor", are curves of ethylene homopolymers prepared in accordancewith the novel, inventive process. The third curve, designated as"Commercial Sample," is a commercially available polyethylene, GUR 4150made by Hoechst Celanese USA.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Catalyst System

Generally, the catalyst system used in the present invention must be atitanium-containing catalyst system, commonly referred to as"Ziegler-Natta" catalysts. Commercially available titanium catalystsystems typically comprise complexes of titanium halides withorganometallic compounds, such as aluminum alkyls. Exemplarymagnesium/titanium catalyst systems include, but are not limited to,those disclosed in U.S. Pat. No.'s. 4,394,291; 4,326,988; and 4,347,158,herein incorporated by reference.

Preferably, the catalyst system is a titanium-containing catalyst and isdeposited on an inorganic oxide support. As used in this disclosure, theterm "support" refers to a carrier for another catalytic component. Anysupport useful to support catalyst systems can be used. Exemplarycatalyst supports include, but are not limited to, inorganic oxides,either alone or in combination, phosphated inorganic oxides, andmixtures thereof. Particularly preferred are supports selected from thegroup consisting of silica, silica-alumina, alumina, fluorided alumina,silated alumina, thoria, aluminophosphate, aluminum phosphate,phosphated silica, phosphated alumina, silica-titania, coprecipitatedsilica/titania, fluorided/silated alumina, and mixtures thereof.Preferably, the catalyst system support comprises silica, titania,alumina, either alone or in combination and either modified orunmodified.

The presently most preferred catalyst system support is asilica-containing support. As used in this application, the reference tosilica means a silica-containing material generally composed of 80 to100 weight percent silica, the remainder, if any, being selected fromalumina, boria, magnesia, thoria, zirconia, or mixtures thereof. Forinstance, the silica-containing material can consist essentially ofsilica and no more than 20 weight percent of alumina, titania or othermetal oxide. Other ingredients which do not adversely affect thecatalyst system, or which are present to produce some unrelated result,also can be present.

As stated previously, the particle size of the polymer fluff iscritical. In accordance with this invention, it has been found that acorrect selection of particle size of the catalyst system particles cancontrol the particle size of the resultant polymer fluff. Usually,catalyst system particles are within a range of about 1 to about 40microns, preferably within a range of about 2 to about 20 microns. Mostpreferably, in order to have a correctly sized polymer product, catalystparticles are kept within a size range of about 4 to about 16 microns.

Titanium usually is present in the catalyst system in an amount within arange of about 0.01 to about 5 weight percent, preferably within a rangeof about 0.1 to about 2.5 weight percent, based on the total mass of thecatalyst system (support plus titanium compound). Most preferably,titanium is present in the catalyst system in an amount within a rangeof 0.2 to 1 weight percent based on the total mass of the catalystsystem for best catalyst system activity and productivity, as well asbest polymer product particle size.

The titanium-containing catalyst is combined, preferably in the reactor,with an aluminum alkyl cocatalyst, expressed by the general formulaeAlR₃, AlR₂ X, and/or AlRX₂, wherein R is an alkyl group having fromabout 1 to about 12 carbon atoms per molecule and X is a halogen atom.Exemplary aluminum alkyl cocatalysts include, but are not limited totriethylaluminum (TEA), triisobutyl aluminum (TIBAL), diethylaluminumchloride (DEAC), ethylaluminum sesquichloride (EASC), and mixtures oftwo or more thereof. Preferably, the cocatalyst is a trialkyl aluminumcocatalyst, such as TEA, TIBAL and mixtures thereof for best catalystsystem activity and reactivity.

If used, a cocatalyst can be present in the reactor in an amount withina range of about 5 to about 500 mg/kg (ppm), based on the weight ofdiluent, such as isobutane in the reactor. Preferably, a cocatalyst, ifused is present in the reactor in an amount within a range of about 50to about 100 mg/kg in order to optimize catalyst activity andproductivity. Precontacting catalyst and cocatalyst can occur, but isnot required. While not wishing to be bound by theory, it is believedthat precontacting catalyst system and cocatalyst can reduce thequantity of cocatalyst used in the reactor.

Reactants

The polymers produced in accordance with the process of this inventionare predominately homopolymers of ethylene. Trace amounts of comonomerscan be present, but comonomers preferably are not present in anysignificant amount since comonomers can reduce the molecular weight ofthe desired ultra high molecular weight polymer product. Preferably, theethylene concentration in the polymerization reactor is within a rangeof from about 2 weight percent to about 15 weight percent, based on thetotal liquid contents of the reactor. Most preferably, the ethyleneconcentration in the polymerization reactor is within a range of fromabout 4 to about 7 weight percent. While ethylene concentration does notsignificantly affect the molecular weight of the resultant polymer,higher or lower ethylene concentration can effect catalyst activity.

Polymerization Process

Polymerization of the monomer must be carried out under loop/slurry,also known as particle form, polymerization conditions wherein thetemperature is kept below the temperature at which polymer swells. Suchpolymerization techniques are well known in the art and are disclosed,for instance, in Norwood, U.S. Pat. No. 3,248,179, the disclosure ofwhich is herein incorporated by reference. A loop polymerization processis much more preferred than a stirred tank reactor because diluent canbe flashed off, eliminating the necessity of separating polymer productfrom solvent, greater heat transfer surface of the loop reactor, muchmore versatility for plant operation, and often less polymer swellingduring polymerization.

The temperature of the polymerization reactor, or reaction zone,according to this invention, is critical and must be kept within a rangeof about 150° F. to about 180° F., preferably within a range of about160° to about 170° F. Most preferably, the reaction zone temperature iswithin a range of 162° to 168° F. The temperature range is critical inorder to produce an ultra high molecular weight polyethylene. Too highof a reactor temperature can produce a polymer with too low of amolecular weight; too low of a reactor temperature can make thepolymerization process inoperable because a lower reactor temperaturecan be difficult to maintain due to the exothermic polymerizationreaction, flashing off reactor diluent can be difficult, and a canproduce a polymer with a commercially unacceptable molecular weight.

The loop/slurry process used in this invention must be carried out in aninert diluent (medium), selected from the group consisting ofhydrocarbons having three and four carbon atoms per molecule. Exemplarydiluents include, but are not limited to propane, n-butane, isobutane,and mixtures thereof. Diluents having greater or less than three or fourcarbon atoms per molecule can be difficult to separate from the polymerproduct during the polymer recovery process. Isobutane is the mostpreferred diluent due to low cost and ease of use.

Pressures in the loop/slurry process can vary from about 110 to about1000 psia (0.76-4.8 MPa) or higher, preferably 500 to 700 psia. Thecatalyst system is kept in suspension and is contacted with ethylene ata sufficient pressure to maintain the medium and at least a portion ofthe ethylene in a liquid phase. The reactor medium and temperature thusare selected such that the polymer is produced and recovered as solidparticles. Catalyst system concentrations in the reactor can be suchthat the catalyst system content ranges from 0.0001 to about 0.1 weightpercent based, on the weight of the reactor contents.

Hydrogen never is added to the polymerization reactor because hydrogenhas too great of an effect on the molecular weight of the resultantpolymer.

Products

Polymers produced in accordance with this invention are considered ahomopolymer of ethylene, even though trace, insignificant amounts ofcomonomers can be present in the resultant polymer. Polymers producedaccording to this invention have an ultra high weight average (M_(w))molecular weight, generally above one million (1,000,000). Preferably,polymers produced in accordance with this invention have a molecularweight within a range of greater than about two million (2,000,000) andmost preferably, within a range of greater than or equal to about2,500,000 up to about 10,000,000.

Since the molecular weight of these polymers is so high, the polymerswill exhibit a value of zero (0) for both the melt index (MI) and highload melt index (HLMI). The inherent viscosity (IV) of the polymersgenerally is greater than about 19, preferably within a range of about20 to about 30. Most preferably, the polymers will have an IV within arange of 22 to 28.

The density of these novel polymers usually is within a range of about0.92 g/cc to about 0.94 g/cc, preferably from about 0.925 to about 0.936g/cc. Most preferably, the polymer density is within a range of about0.927 to about 0.933 g/cc.

Another critical, defining physical characteristic of these polymers isthe fluff, or powder, size. Usually, the particle size is less thanabout 400 microns (40 mesh), preferably within a range of about 400microns to about 40 microns (300 mesh). Most preferably, the particlesize is within a range of about 50 to about 400 microns. Particle sizesof larger that about 400 microns often can appear in the in the finishedproduct as a flaw, or a white patch. While not wishing to be bound bytheory, it is believed that this defect appears because the particlesare not molded by typical methods in the art, but are merely fusedtogether by compression. Fine, or small, particles can inhibit transportof the powder through conveyor blowers because the fine particles cancling to walls by static and can plug downstream filters due toblowover.

Polymers produced according to this invention must be very tough, asevidenced by a sand wheel abrasion test, tensile strength, elongation,flexural modulus, hardness and Izod impact strength. The most importantof these tests is the sand wheel abrasion test wherein a plaque ofcompression molded polymer is subjected to sanding and the amount ofpolymer lost is measured. Generally, the compression molded polymersample loss is less than or equal to about 150 grams, preferably, lessthan about 140 grams. Most preferably, the compression molded polymersample loses between zero (0) and 125 grams.

Polymer tensile strength at yield is within a range of about 15 to about30 MPa, preferably, within a range of about 19 to about 24 MPa. Mostpreferably, as an indicator of toughness, the tensile strength at yieldis within a range of 20 to 24 MPa. Tensile strength at break usually isgreater or equal to about 30 MPa, preferably greater than about 35 MPa.Most preferably, as an indicator of toughness, the tensile strength atbreak is greater than 38 and less than 75 MPa.

Izod impact usually is greater or equal to about 45 kJ/m², preferablygreater than about 50 kJ/m². Most preferably, as another indicator oftoughness, the Izod impact is within a range of about 55 to about 200kJ/m². Izod impact is not only related to the polymer itself, but alsois an indicator of how well the polymer particles fuse, or knit,together during the fusion process. Polymers having too high a molecularweight can have poor Izod impact strength because of poor fusion. Thus,Izod impact strength often can go through a maximum as molecular weightis increased.

Another critical property of these novel, ultra high molecular weightpolymers include physical appearance, such as cleanliness and whiteness.High bulk density also is important because bulk density is related tothe amount of compression of the polymer during fusion. A low bulkdensity can inhibit and slow down processing rates. Generally, polymersproduced in accordance with this invention have a bulk density ofgreater than about 0.25 g/cc, preferably, greater than about 0.3 g/cc.Most preferably, polymer bulk density is within a range of 0.35 to 1g/cc.

A further understanding of the present invention and its advantages areprovided by reference to the following examples.

EXAMPLES Example 1

Ethylene homopolymers were prepared in a continuous particle formprocess by contacting the catalyst with ethylene, employing a liquidfull loop reactor, having a volume of 23 gallons (87 liters), isobutaneas the diluent; no hydrogen or comonomer were added to the reactor. Thereactor was operated to have a residence time of 1.25 hrs. The reactortemperature was 164° F. (73.3° C.), unless stated differently, and thepressure was 4 MPa (580 psi). At steady state conditions, the isobutanefeed rate was 46 1/hr, the ethylene feed rate was about 30 lbs/hr, witha reactor ethylene concentration within a range of about 3.5 to about 5weight percent. Polymer was removed from the reactor at the rate of 22lbs/hr. The catalyst systems used were commercially available catalystsystems purchased from W. R. Grace and Company, the Davison businessunit, designated as Davison Sylopol® 5910, having an average particlesize of 10 microns. Sales literature for Sylopol® 5910 provides achemical analysis (weight percent) of 15.16% Cl, 4.44% Al, 2.95% Mg,0.60% Ti and a Mg/Ti molar ratio of 9.69. Generally, the catalyst systemis a silica-supported Ziegler-Natta catalyst, also described as aZiegler-Natta catalyst deposited on silica. Triethyl aluminum (TEA)cocatalyst was present in the reactor at 50 mg/kg, based on the weightof the isobutane feed.

Polymer product was collected from each run and passed through a 40 mesh(400 micron ) screen to remove large particles. The sieved product wasblended with 0.4 weight percent, based on the weight of polymer, calciumstearate (Ca St) by tumbling. Sieved and CaSt blended samples werecompression molded and tested according to the following procedures:

Density (g/ml): ASTM D 1505-68 and ASTM D 1928, Condition C. Determinedon a compression molded sample, cooled at about 15° C. per minute, andconditioned at room temperature for about 40 hours.

High Load Melt Index (HLMI)(g/10 min): ASTM D1238-95, condition E,determined at 190° C. with a 21,600 gram weight.

Bulk Density (lbs/ft³): ASTM D1895-89.

Tensile Strength ((MPa): ASTM D638-86.

Elongation (%): ASTM D638-86.

Izod Impact, notched (kJ/m²): ASTM D256(a)-84.

Flexural Modulus (MPa): ASTM D790-95a.

Tensile Impact (kJ/m²): ASTM D1822-89.

Sand Wheel Abrasion (grams lost, g): ASTM D65-94. Lower values are moredesirable, as an indication of resistance to abrasion.

Shore D Hardness: ASTM D2240-86.

Intrinsic Viscosity (dl/g): ASTM D4020-92, modified by using 0.015 wt %dissolved polymer rather than 0.05 wt %. The change is made to getbetter dissolution of polymer, which can be difficult to dissolve. Thisprocedure includes a definition of ultrahigh molecular weight polymers.

Molecular Weight Distribution: Molecular weights and molecular weightdistributions were obtained using a Waters 150 CV gel permeationchromatograph with trichlorobenzene (TCB) as the solvent, with a flowrate of 1 mL/minute at a temperature of 140° C. BHT(2,6-di-tert-butyl-4-methylphenol) at a concentration of 1.0 g/L wasused as a stabilizer in the TCB. An injection volume of 220, μL was usedwith a nominal polymer concentration of 0.3 g/l (at room temperature).Dissolution of the sample in stabilized TCB was carried out by heatingat 160-170° C. for 20 hours with occasional, gentle agitation. Thecolumn was two Waters HT-6E columns (7.8×300 mm). The columns werecalibrated with a broad linear polyethylene standard (Phillips Marlex®BHB 5003) for which the molecular weight had been determined.

Polymer properties are given in Table 1.

                  TABLE 1                                                         ______________________________________                                        Property           Result                                                     ______________________________________                                        Density, g/cc      0.931                                                        Bulk Density, lbs/ft.sup.3 24                                                 Tensile Strength, Yield, MPa 22.4 ± 0.3                                    Tensile Strength, Break, MPa 43.7 ± 1.0                                    Elongation, % 232 ± 5                                                      Izod Impact, kJ/m.sup.2 59 ± 3                                             Tensile Impact, kJ/m.sup.2 2545 ± 82                                       Flexural Modulus, MPa 727 ± 26                                             Sand Wheel Abrasion 90 ± 7                                                 Shore D Hardness 70                                                         ______________________________________                                    

The data in Table 1 show that the resultant polymer has desirableproperties, such as a low bulk density, high tensile strength and a lowsand wheel abrasion test result.

Example 2

Polymer was prepared as described in Example 1, but ethyleneconcentration in the reactor was varied from about 2 weight percent toabout 8 weight percent. All other variable remained constant. Theresults are given in Table 2.

                  TABLE 2                                                         ______________________________________                                        Effect of Ethylene Concentration                                                Run            201      202    203    204                                   ______________________________________                                        Ethylene Conc: (wt %)                                                                      2.2      4.75     6.7    7.25                                      Density (g/cc) 0.9317 0.9312 0.9308 0.9311                                    Bulk Density (lbs/ft3) 25.6 24.2 24.2 24.2                                    Avg Particle Size 165 247 251 279                                             (microns)                                                                     Finer than 100 mesh 58 41 37 30.3                                             (wt %)                                                                        Finer than 200 mesh 29 15.8 15.7 10.1                                         (wt %)                                                                        Larger than 35 mesh 1.6 7.7 7.7 8.7                                           (wt %)                                                                        Activity (ppm Ti) 1.1 0.8 0.5 0.5                                           ______________________________________                                    

The data in Table 2 show that ethylene concentration in the reactor doesnot affect polymer molecular weight, as evidenced by density and bulkdensity. However, the polymer particle size varied significantly. Thedata demonstrate that as ethylene concentration increased, the catalystbecame more active and larger polymer particles were produced, asevidenced by particle size distribution measurements. Thus, ethyleneconcentration can be used to control polymer particle size.

Size exclusion chromatography (SEC) results are shown in FIG. I. Thecurve designated as "23 Gallon Reactor" is exemplary for all productsmade in the above-described 23 gallon reactor. All 23 gallon reactorsamples analyzed by SEC have a weight average molecular weight (M_(w))of greater than or equal to about 3,000,000.

Example 3

Another run was made, under similar conditions to those described inExample 1. The same catalyst system described in Examples 1 and 2 wasused in Runs 301-307; the catalyst system used in Runs 311-313 wassimilar to the catalyst system described in Examples 1 and 2, but theparticle size was between 4 and 16 microns; the catalyst system used inRuns 321-326 was similar to the catalyst system described in Examples 1and 2, but the particle size was between 4 and 16 microns and thetitanium level was decreased to make the catalyst less active. Ethyleneconcentration, again, was varied between 0.65 and 10 weight percent andno hydrogen was introduced. Reactor temperatures were about 164° F.,unless stated differently. The results of these runs are given below inTables 3, 4 and 5.

                                      TABLE 3                                     __________________________________________________________________________    Effect of Ethylene Concentration with Sylopol ® 5910                      Run         301  302  303  304  305  306  307                                 __________________________________________________________________________    Ethylene Conc: (wt %)                                                                     0.65 2.0  2.5  3.8  4.9  7.5  8.9                                   Density (g/cc) 0.9327 0.9316 0.9318 0.9308 0.9310 0.9310 0.9308                                                        Bulk Density (lbs/ft.sup.3)                                                  23.4 25.2 24.2 25.6 24.5 23.4                                                 24.2                                  Avg Particle Size (microns) 81 140 172 156 193 257 226                        Finer than 100 mesh (wt %) 87.0 80.0 65.3 60.5 69.7 44.1 48.5                 Finer than 200 mesh (wt %) 69.0 29.4 23.6 29.6 16.8 9.7 10.3                  Larger than 35 mesh (wt %) 0.32 0.9 1.89 1.61 4.0 8.0 3.8                     Activity (ppm Ti) 9.7 2.2 1.3 1.0 0.6 0.4 0.4                               __________________________________________________________________________

                  TABLE 4                                                         ______________________________________                                        Effect of Ethylene Concentration with Specifically Tailored                     Catalyst (4-16 Micron and Low Titanium)                                       Run             311        312    313                                       ______________________________________                                        Ethylene Conc: (wt %)                                                                       4.5        6.9      10.6                                          Density (g/cc) 0.9320 0.9319 0.9319                                           Bulk Density (lbs/ft.sup.3) 26.3 26.6 25.2                                    Avg Particle Size (microns) 164 220 163                                       Finer than 100 mesh (wt %) 66.6 31.5 65.6                                     Finer than 200 mesh (wt %) 6.9 7.6 7.6                                        Larger than 35 mesh (wt %) 0.54 1.39 0.68                                     Activity (ppm Ti) 1.2 0.6 0.9                                               ______________________________________                                    

                                      TABLE 5                                     __________________________________________________________________________    Effect of Reactor Temperature                                                 Run       321  322  323  324  325  326                                        __________________________________________________________________________    Ethylene Conc: (wt %)                                                                   4.5  4.0  3.4  3.4  4.5  5.3                                          Temperature °F. 164 174 185 205 220 225                                Density (g/cc) 0.9322 0.9339 0.9378 0.9412 0.9433 0.9435                      Bulk Density 27.0 25.9 26.6 27.0 28.5 28.8                                    (lbs/ft.sup.3)                                                                Avg. Particle Size 199 206 245 263 266 267                                    (microns)                                                                     Particles finer than 100 34 30 22 13.5 13 17                                  mesh (%)                                                                      Particles finer than 200 8.1 6.6 4.2 2.3 2.8 3.6                              mesh (%)                                                                      Particles larger than 35 0.43 0.38 1.25 0.48 0.58 1.85                        mesh (%)                                                                      Activity (ppm Ti) 0.8 0.7 0.4 0.2 0.2 0.4                                   __________________________________________________________________________

The data in Table 3 demonstrate the effects of ethylene concentration onpolymer density, bulk density and average polymer particle size.

The data is Table 4 show that the effect of ethylene concentration witha catalyst system having a particle size within a range of 4 to 16microns and low titanium content.

The data in Table 5 show the effect of reactor temperature and thathigher temperatures can increase polymer density.

Example 4

Ethylene homopolymers were prepared in a continuous particle formprocess by contacting the catalyst with ethylene, as described above,but a larger reactor was used. The liquid full loop reactor had a volumeof 600 gallons (2271 liters), isobutane was the diluent; no hydrogen orcomonomer were added to the reactor. The reactor was operated to have aresidence time of about 1.25 hrs. The reactor temperature was 164° F.(73.3° C.), unless stated differently, and the pressure was 4.14 MPa(600 psi). Polymer was removed from the reactor at the rate of 800 to1000 lbs/hr. The catalyst systems used were the same as those describedabove, Davison Sylopol® 5910. Triethyl aluminum (TEA) cocatalyst waspresent in the reactor at 75 mg/kg, based on the weight of the isobutanefeed.

Polymer product was collected from each run and treated as describedabove. Polymer product then was analyzed for physical properties,however sample preparation was different than described above. For Runs401-403, a polymer plaque was prepared by pressing 460 grams of polymerat 420° F. for 60 minutes, then cooling for 30 minutes, all at 1000 psi.Intrinsic viscosity (IV) was determined as described above. The resultsof the analyses are listed below in Table 6.

                                      TABLE 6                                     __________________________________________________________________________    Ultrahigh Molecular Weight Polyethylene Properties                                                    Commercial                                                                          Commercial                                        Property Run 401 Run 402 Run 403 Sample A.sup.(a) Sample B.sup.(b)          __________________________________________________________________________    Density, g/cc                                                                         0.932 0.932                                                                              0.931                                                                              0.932 0.929                                             Tensile Strength, 21.2 20.0 19.8 22 20.4                                      Yield, MPa                                                                    Tensile Strength, 36.4 34.6 35.0 41.7 39.9                                    Break, MPa                                                                    Elongation, % 240 228 211 287 345                                             Izod Impact, 59 63 50 55.3 90.6                                               kJ/m.sup.2                                                                    Tensile Impact, 2334 2290 2283 1890 2400                                      kJ/m.sup.2                                                                    Flexural 770 804 772 712 606                                                  Modulus, MPa                                                                  Flexural 770 804 772 712 606                                                  Strength, MPa                                                                 Sand Wheel 107 107 108 106 96                                                 Abrasion                                                                      IV, 1st analysis 23.7 25.1 24.4 N/A N/A                                       IV, 2d analysis 24.9 23.7 24.3 N/A N/A                                        IV, average 23.2 19.7 21.4 28 27                                            __________________________________________________________________________     .sup.(a) Sample is 1900CM, made by Montell USA.                               .sup.(b) Sample is GUR 4150, made by Hoechst Celanese USA.                    N/A = not available                                                      

The data in Table 6 shows that polymers produced in accordance with theinvention have high inherent viscosity (IV) values and are polymers ofethylene having ultrahigh molecular weights.

Size exclusion chromatography (SEC) results are shown in FIG. I. Thecurve designated as "600 Gallon Reactor" is exemplary for all productsmade in the above-described 600 gallon reactor. All 600 gallon reactorsamples analyzed by SEC have a weight average molecular weight (M_(w))of greater than or equal to about 2,500,000. Note that the curvedesignated as a "Commercial Sample" had a similar SEC curve as that ofthe 600 gallon reactor sample.

While this invention has been described in detail for the purpose ofillustration, it is not to be construed as limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed is:
 1. A loop/slurry polymerization processcomprising contacting in a reaction zone, at a temperature within arange of about 150° F. to about 180° F. in the presence of a hydrocarbondiluent having three or four carbon molecules per molecule, and in theabsence of hydrogen:a) ethylene monomer; b) a catalyst system comprisinga magnesium compound and a titanium halide, wherein both the magnesiumcompound and the titanium halide are supported on an inorganic oxidesupport and said catalyst system has a particle size within a range ofabout 1 to about 40 microns; and c) an aluminum alkyl cocatalyst; andrecovering a homopolymer of ethylene, wherein said homopolymer ofethylene has a weight average molecular weight greater than about onemillion (1,000,000) and a high load melt index of 0 g/10 minutes.
 2. Aprocess according to claim 1 wherein said reaction zone temperature iswithin a range of about 160° F. to about 170° F.
 3. A process accordingto claim 1 wherein said inorganic oxide support is selected from thegroup consisting of silica, silica-alumina, alumina, fluorided alumina,silated alumina, thoria, aluminophosphate, aluminum phosphate,phosphated silica, phosphated alumina, silica-titania, coprecipitatedsilica/titania, fluorided/silated alumina, and mixtures thereof.
 4. Aprocess according to claim 3 wherein said inorganic oxide is asilica-containing support selected from the group consisting of silica,silica-alumina, phosphated silica, silica-titania, coprecipitatedsilica/titania, fluorided/silated alumina, and mixtures thereof.
 5. Aprocess according to claim 4 wherein said support is essentially silica.6. A process according to claim 1 wherein said catalyst system particlesize is within a range of about 2 to about 20 microns.
 7. A processaccording to claim 6 wherein said catalyst system particle size iswithin a range of about 4 to about 16 microns.
 8. A process according toclaim 1 wherein said aluminum alkyl cocatalyst has the general formulaeAlR₃, AlR₂ X, or AlRX₂, wherein R is an alkyl group having from about 1to about 12 carbon atoms per molecule and X is a halogen atom.
 9. Aprocess according to claim 8 wherein said aluminum alkyl cocatalyst isselected from the group consisting of triethyl aluminum,triisobutylaluminum chloride, diethyl aluminum chloride, ethylaluminumsesquichloride, and mixtures thereof.
 10. A process according to claim 9wherein said aluminum alkyl cocatalyst is selected from the groupconsisting of triethyl aluminum, triisobutyl aluminum and mixturesthereof.
 11. A process according to claim 1 wherein said aluminum alkylcocatalyst is present in the reactor in an amount within a range ofabout 5 to about 500 mg/kg, based on the mass of hydrocarbon diluent inthe reactor.
 12. A process according to claim 1 wherein said catalystsystem and aluminum alkyl cocatalyst are contacted prior to contactingsaid ethylene.
 13. A process according to claim 1 wherein said diluentis isobutane.
 14. Process according to claim 1 wherein said homopolymerof ethylene comprises a polymer having:a) a weight average molecularweight greater than about one million; b) an inherent viscosity greaterthan about 19; c) a particle size less than about 400 microns; c) adensity within a range of about 0.92 g/cc to about 0.94 g/cc; d) a highload melt index of 0 g/10 minutes; e) a sand wheel abrasion loss asdetermined by ASTM D65-94 of less than about 150 grams.